Basic anthraquinone dyestuffs

ABSTRACT

The invention relates to basic dyestuffs that are free from acidic groups imparting solubility in water which contain at least one etherified hydroxylamino residue which is linked through the nitrogen atom to a carbon atom of the dyestuff molecule, the corresponding quaternated dyestuffs and double salts thereof.

United States Patent Hegar et al.

[ Jan. 14,1975

BASIC ANTHRAQUINONE DYESTUFFS Inventors: Gert Hegar, Schoenenbuch;

Visvanathan Ramanathan, Basel, both of Switzerland Assignee: Ciba-GeigyAG, Basil, Switzerland Filed: July 15, 1971 Appl. N0.: 163,086

Related US. Application Data Division of Ser. No. 717,011, March 28,1968, Pat. No. 3,627,751.

Foreign Application Priority Data Apr. 4, 1967 Switzerland 4743/67 US.Cl 260/378, 8/39, 8/40, 260/380 Int. Cl. C09b 1/28, C09b l/32, COlb H50[58] Field of Search 260/380, 378

[56] References Cited UNITED STATES PATENTS 3,627,751 l2/l97l Hegar etal. 260/205 Primary ExaminerRobert Gerstl Attorney, Agent, or FirmJosephG. Kolodny; Edw. McC, Roberts; Prabodh I. Almaula [57] ABSTRACT 4Claims, No Drawings BASIC ANTHRAQUINONE DYESTUFFS This a division ofapplication Set. No. 717,011, filed Mar. 28, 1968 now US. Pat. No.3,627,751.

The present invention provides new dyestuffs that are free from acidicgroups imparting solubility in water, particularly sulphonic acid andcarboxylic acid groups, and contain at least one etherifiedhydroxylamino residue which is linked through the nitrogen atom with acarbon atom of the dyestuff molecule and the corre sponding quaternateddyestuffs. It is primarily concerned with dyestuffs of the formula inwhich A represents the residue of a dyestuff which is free fromsulphonic acid and carboxylic acid groups, Y represents a linear orbranched aliphatic carbon chain having up to 4 carbon atoms, R and Reach represents hydrogen or an alkyl, aralkyl or cycloalkyl residue, Ran alkyl, aralkyl or cycloalkyl residue, X represents an anion and n lor 2, and in which N, R and Y or N, R and R or N, R and OR may formmembers of a heterocycle.

The new dyestuffs may be prepared according to this invention byamidation or condensation, coupling or quaternation.

l N-O l R3 in which R R and R have the above meanings. Alternatively, acompound of the formula (3) z' Y -1i o R3 R2 X- n l in which R R and RX, Y and n have the above meanings and Z stands for a reactive atom or amac tive group, e.g. a halogen atom, a sulphato group, an amino group, acarboxylic acid chloride orsulphonic acid chloride group, may be reactedwith a compound of the formula AZ", in which A is a dyestuff residue andZ" a reactive atom or a reactive group that is capable of reacting withZ.

in the manufacture by coupling, which applies to azo dyestuffs, a diazocompound may be coupled with a coupling component, of which at least onemust contain the abovementioned etherified hydroxylamino residue,preferably the residue of the formula in which R,, R and R;,, X, Y and nhave the meanings defined above.

In the manufacture by quaternation the corresponding dyestuffscontaining an unquaternated cthcrified hydroxylamine residue are treatedwith quaternating reagents, e.g. dyestuffs of the formula (l where n =1and A, Y, R, and R have the above meanings-may be reacted with compoundsof the formula R X,-in which X has the meaning defined above and Rrepresents an alkyl, aralkyl or cycloalkyl residue.

The dyestuff radical A may be that of a dyestuff of any one of thefollowing'series: nitroso, nitro, styryl, stilbene, dior triarylmethane,methinc, polymcthinc, sulphur, anthraquinone, quinoimine, azine,oxazine, thiazine, perinone, naphthoquinone, indigo, quinophthalone,pyrazolone, xanthene, acridine, quinoline, cy anine, phthalocyanine,azomethine or especially the mono-, disor polyazo series. As suitableanthroquinone dyestuff radicals there may be mentioned e.g. those of theformula in which R represents a lower alkyl or an aryl radical e.g. amethylene or phenylene group, X stands for an NH or OH group and X and Xeach represents hydrogen, or an NH OH or NO group, or thoseanthroquinones which contain further substituents in ortho-position toone of the groups X or N- H-R-, e.g. halogen, alkyl or alkoxy.

In the anthraquinonc dyestuff series the following may be mentioned asbeing suitable for the reaction with the etherified hydroxylamine; inthese formulae Z has the meaning defined above and stands moreespecially for a chlorine atom or for a sulphato, arylsulphonyloxy oralkylsulphonyloxy group.

3 so 10 rtac n z lo mrc a z i l l H2N 0 on 0 on terials may be mentioned(in which Z has the above meaning):

As examples of styryl dyestuffs the following may be mentioned in which2 also has the above meaning:

Suitable azo dyestuffs are those which have been prepared by couplingdiazotized amines, preferably of the aromatic or heterocyclic series,with any desired coupling components, of which at least one componentmust contain a reactive atom or a reactive group Z or Z as definedabove. A list of suitable diazo and coupling components is given furtheron in connection with the description of the manufacture by coupling.

According to process (a) of the present invention starting dyestuffs arereacted with quaternated or unquaternated etherified hydroxylamines ofthe formula (2) or (3). As such compounds the following for instance maybe mentioned:

carried out with dyestuff intermediates instead od with the dyestuffs,and from the resulting reaction products the final products are obtainedby coupling or condensation. This variant is particularly suitable forthe manufacture of azo dyestuffs. For this purpose a diazotized amine iscoupled with a coupling component; either the diazo component or thecoupling component must contain the etherified hydroxylamine residue.

As examples of diazo components aromatic compounds may be particularlymentioned eg. those of the napthalene or especially of the benzeneseries. The latter correspond e.g. to the formula in which X, representsa hydrogen or halogen atom, or a cyano, carbalkoxy, alkanesulphonylsulphonamide, phenylazo or nitro group, Y,,- represents a hydrogen orhalogen atom or a nitro, alkyl, alkoxy, trifluoro methyl, carbalkoxy orcyano group, Z represents a hydrogen or halogen atom, and at least oneof the residues X or Y; must stand for a halogen atom or rat-0on ftfl-ocn I\iOCH CH CH en err OH HN CH 21 a cs I 3 2 2 1 l l I N-O--CH CH 0 OH Hc N t CH 2 2 c3 HN-OC ha H3 (1 CH3 H 0 CH Cl N 2H5 l CH I 2 C11 2 Oc IClQO CH CH OCH H C\ /CH I Gri O--CH ca -so 0-011 CH N I 2 2 2 7 CH -CHThe reaction of the dyestuff containing e.g. a halogea nitro,carbalkoxy, cyano, alkylsulphonyl, sulnoor sulphatoalkyl group, with theetherified hydrox- 35 phonamide or phenylazo group. ylamine is carriedout inaneutral solvent e.g. in chloro- As examples f Suitable diazocomponcms f the benzene, alcohol Flqueous alcohol mixture or in benzeneseries the following may be mentioned: anidimethylformamide, or in theabsence of solvents, adline, or 4 chlorobenzene vantageously at anelevated temperature in an excess of bmmobenzene, 1 i 2 or 4mcthylbcnzcnc the hydroxylamine and, if desired, in the presence of a 40or Amitmbenzene Catalyst, Sodium lodldecyanobenzene, l-aminobenzene-3-or -4- According to process (b) of the present invention themethylsulphone l amino z chlombcnzcnc 4 reaction with the etherifiedhydroxylamines may be methylsulphone 1 aminO 2jdkwmbenzcnc1-amino-4-carbethoxybenzene, l-amino-2,4- or -2,5- dichlorobenzene,l-amino-2,4-dibromobcnzene, l-amino-2-methyl-4- or 6-chlorobenzenc,l-amino2- trifluoromethyl-4-chlorobenzene, l-amino2cyuno-4-chlorobenzene, l-amino2-cyano-4-nitrobenzenc,lamino-2-carbomethoxy-4-chlorobcnzenc, l-amino-Z-methanesulphonyl-4-chlorobenzene, l-amino-Z-carbomethoxy-4-nitrobenzene, l-amino-2-phenoxy-4- nitrobenzene,l-amino-2-chloro-4-cyunobenzcne, l amino-2-chloro-4-nitrobenzene,l-amino-Z-mcthoxy- 4-nitrobenzene, l-amino-2-chloro-4-curbethoxybenzene,1-amino-2,4-dinitrobenzene, l-amino-2,4 dicyanobenzene,l-amino-2,6-dichloro-4- cyanobenzene,l-amino-2,6-dichloro-4-nitrobcnzenc, l-amino-2,5- or-2,6-dichlo'robenzene-4-sulphonic acid dimethylamide,l-amino-2-chlorobenzene-4-sulphonic acid dimethylamide,l-amino-2,6-dibromobcnzcne-4 sulphonamide,l-amino-2,4-dinitro-6-chloroor -6- bromobenzene, l-amino-2,4-dicyuno-6-chlorobenzene, 1-amino-2,4,6-trichloroor -tribromobenzene,l-aminobenzene-3 or -4-sulphonamide, 1-aminobenzene-3- or -4-sulphonicacid-N- methylamide or -diethylamide, 4-aminouzobcnzcnc,4-amino-2-chloro-azobenzene, 4-amino-2,4- dichloro-azobenzene,4-amino-3-chloro-azobenzenc,

azobenzene, 4-amino-3 -nitro-azobenzene, 4-amino-2-methyl-azoben2ene,4-amino-4 methoxyazobenzene, 4-amino-3-nitro-2- 4-amino-3-nitro-4'-chloroazobenzene, 4-amino-3-nitro-2', 4- dichloroazobenzene,4-amino-3-nitro-4- methoxyazobenzene, 4-aminodiphenyl and 2- or 4-aminodiphenyl ether.

Further suitable diazo components are any desired diazotisableheterocyclic amines that are free from acidic substituents impartingsolubility in water, and especially amines containing a S-memberedheterocycle with 2 or 3 hetero atoms, above all one nitrogen atom andone or two sulphur, oxygen or nitrogen atoms as hetero atoms.

From the series of heterocyclic diazo components the following may bementioned as examples: 2- aminothiazole, 2-amino-5-nitrothiazole,2-amino-5- methylsulphonylthiazole, 2-amino-5-cyanothiazole, 2-amino-4-methyl-5-nitrothiazole, 2-amino-4- methylthiazole2-amino-4-phenylthiazole, 2-amino-4- (4'-chloro)-phenylthiazole,2-amino-4-(4'-nitro)- chloroazobenzene,

phenylthiazole, 3-aminopyridine, 3-aminoquinoline, 3-aminopyrazole,3-amino-l-phenylpyrazole, 3- aminoindazole, 3-aminol,2,4-triazole,3-amino-l-(4'- methoxyphenyl)-pyrazole, Z-aminobenzthiazolc,

2-amino-6-methylbenzthiazole, 2-amino-6- methoxybenzthiazole,2-amino-6-chlorobcnzthiazole, 2-amino-6-cyanobenzthiazole, 2-amino-6-nitrobenzthiazole, 2-amino-o-carbethoxybenzthiazole,2-amino-6-methylsulphonylbenzthiazole, Z-aminol,3,4-thiadiaz0le,2-amino1,3,5-thiadiazole, Z-amino- 4-phenylor 4-methyl-l,3,5-thiadiazole and 2-amino-5- phenyl-l ,3,4-thiadiazole.

When the above-mentioned diazo components are to be used, the etherifiedhydroxylamino group must be present in the coupling component, unless itis to be subsequently introduced by condensationv As examples of suchcoupling components the following compounds may be mentioned; in theformulae shown 0 represents a quaternated or unquaternated etherifiedhydroxylamino group linked through the nitrogen atom or, when this groupis to be subsequently introduced by condensation according to theprocess (a) of the invention, it represents a reactive atom or areactive group, e.g. a halogen atom, a sulphato group or anarylsulphonyloxy or alkylsulphonyloxy group:

When a coupling component is used that does not contain an etherifiedhydroxylamino group, this group must be present in the diazo componentunless it is subsequently introduced by condensation. As such diazocomponents there may specially mentioned aminobenzenes ofthe formula l\LO- l'-allC-CO-.-'l-NH in which X, n and R R and R have the samemeanings as in formula (1), alk represents an alkylene bridge and A abenzene nucleus which may carry substituents, e.g. halogen atoms, nitroor lower alkyl or alkoxy groups. As examples of quaternated derivativesthe fol lowing compounds may be mentioned: 4-amino-a-(N-chloro-N,N-dimethyl-N-methoxyamino)- acetophenone,4-amino-a-(N-chloro-N,N-diethyl-N- ethoxyamino)-acetophenone,4-amino-a-(N-chl0r0-N- methoxypiperidino)-acetophenone,4-amino-3-methyla-(N-chloro-N,N-dimethyl-N-methoxyamino)- acetophenone,.4-amino-3-methoxy-a-(N-chloro-N,N-dimethyl-N-methoxyamino)-acetophenone, 4-amino-3-chloro-a-(N-chloro-N,N-dimethyl-N- 1 methoxyamino)-acetophenone,4-amino-3-bromo-a- (N-chloro-N,N-dimethyl-N-methoxyamino)- acetophenone,

4-amino-2-chloro-a-(N-chloro-N,N-

Further suitable are diazo components that contain an etherifiedhydroxylamino group, including those of the general formula in which Vrepresents a nitro, alkylsulphonyl or unsubstituted or substitutedsulphonamide group, W represents a bivalent residue e.g. an Oor S bridgeor a direct bond, and R R and R X, Y and n have the same meanings as iformul (1), d i hi h h 5 the benzene series there may be mentioned,apart from benzene residue may contain further substituents. As thePhenols, for example Pam-@650], especially the such diazo c onent th mayb i d, for aminobenzenes, for example aniline, 3-methylaniline, example,the compounds of the formulae 2"methOXy-5-mthylani]inc, 3-ilcctylilmim)T laminobenzene, N-methylanilinc, N-B- E CH l0 hydroxyethylaniline,N-B-methoxyethylanilinc, NB- A cyanoethylaniline,N-B-chloroethylaniline, dimethylan- OCH CH2N OCH iline, diethylaniline,N-methyl-N-benzylanilinc, N-n- 9 butyl-N-B-chloroethylaniline,N-methyl-N-B- Cl cyanoethylaniline, N-methyl-N-B-hydroxyethylaniline,

3 l5 N-ethyl-N-B-chloroethylaniline, N-methyl-N-B- acetoxyethylaniline,N-ethyl-N-B-mcthoxyethylzmilinc, C oN-B-cyanoethyl-N-Bchloroethylaniline, N-cyanoethyl- 3 2N-acetoxyethylaniline, N,N-di-B-hydroxycthylaniline,

N,N-di-B-acetoxyethylaniline, N-ethyl-N,2-hydroxy-3- T 2Ochloropropylaniline, N,N-di-B-cyanoethylaniline, N,N-OCHZ(SHZIM-OCJIIZ'CF di-B-cyanoethyl-3-methylaniline, N,B'-cyanoethyl-N-L CH B"-hydroxyethyl-3-chloroaniline, N,N-di-B- 3 3 Jcyanoethyl-3-methoxyaniline, N,N-dimcthyl-3- acetylaminoaniline,N-ethyl-N-B-cyunoethyl-3- or acetylaminoaniline,N,N-di-B-cyanoethyl-2-methoxy- S-acetylaminoaniline,N-methyl-N-phenacylaniline, N B-cyanoethyl-2-chloroaniline,N,N-diethyl-3- trifluoromethylaniline, N-ethyl-N-phenylaniline, diphe- W2 nylamine, N-methyldiphenylamine, N-methyl-4- OCa CH N 6ethoxydiphenylamine or N-phenylmorpholine, and \C'H also, for example,amines of the formula 0 N 2-11 2 2 2 RI Cl Y 2 P Also suitable are diazocomponents that contain an Y etherified hydroxylamino group, includingthose of the z}. general formula 1 40 in which R, represents a hydrogenatom or an alkyl or 1 alkoxy group, R a cyanoalkoxyalkyl group, R a hy-B O I? Y lv' N13 drogen atom or a cyanoalkoxyalkyl or acyloxyalkylgroup, and R represents a hydrogen atom or an un- X 2M1 substituted orsubstituted alkyl, cycloalkyl or alkoxy 2 group or a benzene residue,and especially those of the formula in which W represents a bivalentorganic residue e.g. an SO SO NR CONR or COO L r bridge and R R and R X,Y and n have the same l /CH CH OCH CH CN meanings as in formula (1), andR represents a hydrogen atom or an alkyl, cycloalkyl, aralkyl or arylgroup. W As examples of such diazo components there may be mentioned: '4

3 fz s Ch O-I\-Cfl Ch SO I EH 0 1-1 olilqffkcfl hnSO -gfflh H A c1 thecoupling component used may be of any desired kind and may belong eg tothe benzene or naphthalene series or to the series of the heterocycliccoupling components. From among the coupling components of in which R,and R have the above meanings.

Valuable results are also obtained with coupling components of theformula in which R, has the above meaning and X represents an acylaminogroup, and in which the alkyl group may be, for example, methyl, ethylor propyl.

As relevant examples of coupling components the following compounds maybe mentioned: 25 ing to this invention and instead of a single couplingOCH OC 1'I -N- CH CH OCH Ch CN) 2 w (CH CH OCH CH CM 2 NHCOCH NHCHO OCHr T "\T L s Q-lmen ca oca ca cu CH CH COCH- "HUOCEL 9 NHCOCH part1IE-ICI-I C H OCH CEI CI? QIGICH GH OCH CH CN l V ZTrZCOCH KHCOCH 3 OCHOCH I @LiC-ICH GH 0COCH gBfNHCH CH OCH CH CN 13100011. KEY-16003 35,

component a mixture of two or more of the couplingcomponents may be usedaccording to this invention. W W The said diazo components may bediazotized by 1fher-I2CH OCI1 Cd Cu 60 known methods, e.g. with amineral acid, especially hy- I drochloric acid, and sodium nitrite or,for example, H with a solution of nitrosylsulphuric acid in concen- Thecoupling components of the naphthalene series which may be mentioned,apart from thenaphthols are, for instance 1- or 2-naphthylamine and 2-phenylaminonaphthalene, ldimethylaminonaphthalene and 2-ethylaminonaphthalene.

As examples of heterocyclie coupling components the indoles may bementioned"'foi example 2- methylindole, 2,5-dimethylindole, Zildimethyl-l methoxyindole, 2-phenylor 2-methyl-5-ethoxyindole,2-methyl-5- or -6-chloroindole, l,2-dimethylindole,l-methyl-2-phenylindole, 2-methyl-5-nitroindole, 2-methyl-5-cyanoindole,2-methyl-7-chloroindole, 2-methyl-5-fluoroor -5-bromoindole,2-methyl-5',7-

dichloroindole or 2-phenylindole, I-'cyanoethyl2,6-

dimethylindole; also pyrazoles e.g. l-phenyl-S- aminopyrazole or3-methyl-pyrazolone-5 or l-phenyl- 3-methyl-pyrazolone-5, l,3dimethylpyrazolone-5, lbutyl-3-methyl-pyrazolone-5, l-hydroxyethyl3-methylpyrazolone-S, l-eyanoethyl3-methyl pyrazolone-S,l-(orthoehlorophenyl)-3-methylpyrazolone-S, 3-carbomethoxy-pyrazolone5;quinolines for example 1-methyl4-hydroxy-quinolone-2, N-ethyl-3-hydroxy-7-methyl l ,2,3 ,4,- tetrahydroquinoline, or pyrimidinesfor example barbiturie acid and 1,3-indandione, 1,8-naphthindandione ordimedone.

Instead of a single diazo component a mixture of two or more of thediazo components may he used accordtrated sulphuric acid.

Coupling may also be carried out in known manner e.g. in a neutral,basis or acidic medium ifdesired in the presence of sodium acetate orsimilar buffer substances that affect the rate of coupling, or ofcatalysts e.g. pyridine or a salt thereof.

Any of the new dyestuffs that contains a quaternated etherifiedhydroxylamino group can be prepared according to process (c) of thepresent invention by quaternating the corresponding dyestuffs thatcontain an etherified hydroxylamino group which may be alkylated at thenitrogen atom my treatment with an alkylating agent. As such alkylatingor quaternating agents there may be used e.g. esters of strong mineralacids or organic sulphonic acids, for instance dimethyl sulphate,diethyl sulphate, alkylhalides e.g. methyl chloride, bromide or iodide,aralkyl halides e.g. benzyl chloride, or esters of lower alkanesulphonic acids e.g. methyl esters of methane sulphonic, ethanesulphonic or butane sulphonic acid, or esters of benzene sulphonic acidswhich may contain additional substituents e.g. methyl, ethyl, propyl orbutyl esters of benzene sulphonic acid, 2- or 4-methylbenzene sulphonicacid, 4-chlorobenzene sulphonic acid or 3- or 4-nitrobenzene sulphonicacid.

The alkylation is advantageously carried out by heating in an inertorganic solvent e.g. a hycrocarbon for example benzene, toluene orxylene, or a halogenated hydrocarbon for example carbon tetrachloride,tetrachloroethane, chlorobenzene, orthodichlorobenzene, or anitrohydrocarbon for example nitromethane, nitrobenzene or anitronaphthalene. Solvents also suitable for the alkylation are acidanhydrides, acid amides and nitriles for example acetic anhydride,dimethyl-formamide or acetonitrile or dimethylsulphoxide. lnstead of asolvent a substantial excess of aklylating agent may be used, but insuch a case it must be ensured that the reaction mixture does notoverheat because the reaction is strongly exothermic. Nevertheless it isin most cases necessary, especially in the presence of an organicsolvent. to supply external heat to the reaction mixture to trigger offthe reaction. In special cases the alkylation may also be carried out inan aqueous medium or in an alcohol, if desired, in the presence of asmall quantity of potassium iodide.

The dyestuff salts may be purified if necessary, by dissolvingadvantageously in water, whereupon any un reacted starting dyestuff canbe filtered off in the form of an insoluble sediment. On addition of awatersoluble salt, for example sodium chloride, to the solution thedyestuff can again be isolated.

The anion present in the quaternated dyestuff obtained by the presentinvention is preferably the residue of a strong acid, for example ofsulphuric acid or a semi-ester thereof, or an arylsulphonic acid, or itmay be a halogen ion. The said anions, which according to this inventionare introduced into the dyestuff molecule, may be replaced, if desired,by anions of other inorganic acids, for example of phosphoric orsulphuric acid, or organic acids e.g.- formic, lactic or tartaric acid;if desired, the free bases may be used in certain cases. The dyestuffsalts may also be used in the form of double salts, for example with thehalides of the elements of group II of the Periodic Table, especiallywith zinc chloride or cadmium chloride.

The new dyestuffs or dyestuff salts containing a quaternated amino groupare suitable for dyeing or printing a wide variety of fully syntheticfibers, for example of polyvinylchloride, polyamide or polyurethanefibres, also fibres of polyesters of aromatic dicarboxylic acids e.g.polyethylene terephthalate fibres but particularly polyacrylonitrilefibres or polyvinylidene-cyanide fibres (Darvan). The termpolyacrylonitrile fibres re fers in the first place to polymerscontaining more than 80% e.g. 80 to 95%, of acrylonitrile; in addition,they contain 5 20% of vinyl acetate, vinyl-pyridine, vinyl chloride,vinylidene chloride, acrylic acid, acrylic acid esters, methacrylicacid, methacrylic acid esters or the like. These products are marketed,for example, under the following trademarks: Acrilan I656" (TheChemstrand Corp., Decatur, Alabama,), Acrilan 4l (The Chemstrand Corp),*Creslan" (American Cyanamide Company), Orlon 44" (Du Pont), Crylor HH(Soc. Rhodiaceta SA. France), Leacril N" (Applicazioni Chimice Societaper Azioni, ltaly), Dynel" (Union Carbide Chem. Corp), Exlan (Janpan,Exlan Industry Co., Japan), Vonnel (Mitsubischi, Japan), Verel(Tennessee Eastman, U.S.A.), Zefran (Dow Chemical, U.S.A.), Wolcrylon"(Filmfabrik Agfa, Wolfen, East Germany), Ssaniw (U.S.S.R.), and alsoOrlon 42, Dralonf Courtelle" and the like.

The quaternated, water-soluble dyestuffs are in general practicallyinsensitive to electrolytes and some of them are very readily soluble inwater or in polar sol vents. Dyeing with the quaternated water-solubledyestuffs is in general carried out in an aqueous, neutral or acidicbath, at the boil under atmospheric, or under superatmospheric pressureat an elevated temperature. The commerical levelling agents do notaffect the dyeing operation, but they are not needed.

The new dyestuffs are also particularly suitable for three colourdyeing. Furthermore, by virtue of their stability towards hydrolysisthey may be used with advantage for high temperature dyeing and fordyeing in the presence of wool. They may also be used for printing,using, for example, a printing paste that contains the dyestuff and theassistants conventionally used in dyeing. Furthermore, they may be usedfor dyeing acrylonitrile polymers in bulk and also other plastic masseswhich may be dissolved, to produce shades that are fast to light andwashing, and also for colouring oil paints and lacquers, or for dyeingcotton, especially mordanted cotton, cellulose, regenerated celluloseand paper.

The new water-insoluble dyestuffs prepared according to this invention,which contain a tertiary ctherified hydroxylamino group, areadvantageously applied in a finely disperse form in the presence ofdispersants for example soap, cellulose waste sulphite liquor orsynthetic detergents, or of acombination of different wetting anddispersing agents. As a rule it is advantageous to convert thesedyestuffs before the dyeing operation into a dye preparation thatcontains a dispersant and the finely dispersedyestuff in such a formthat when the dye preparation is diluted with water a fine dispersion isobtained. Such dye preparations may be manufactured in known manner e.g.by reprecipitating the dyestuff from sulphuric acid and grinding theresulting suspension with sulphite waste liquor, or alternatively bygrinding the dyestuff in a highly efficient mill in the dry or wet form,with or without addition of a dispersant during grinding. They are alsosuitable for dyeing or printing a wide variety of semi-synthetic orfully synthetic fibres e.g. cellulose acetate fibres, polyolefine fibresfor example modified polypropylene, polyacrylonitrile,polyvinylchloride, polyamide or polyurethane fibres, and above allfibres of polyesters of aromatic dicarboxylic acids, e.g. polyethyleneterephthalate fibres.

When strong dyeings, e.g. on polyethylene terephthalate fibres, aredesired, it is advantageous to add to the dyebath a swelling agent, orto dye under superatmospheric pressure at a temperature above 100C, forexample at 120C. Suitable swelling agents are aromatic carboxylic acids,for example benzoic or salicylic acid, phenols, for example orthoorparahydroxydiphenyl, aromatic halogen compounds, for examplechlorobenzene, ortho-dichlorobenzene or trichlorobenzene,phenylmethylcarbinol or diphenyl. When dyeing under superatmosphericpressure it is advantageous to render the dyebath slightly acidic byadding e.g. a weak acid for example acetic acid.

The new dyestuffs containing a tertiary etherified hydroxylamino groupare specially suitable for dyeing by the so-called thermofixation methodin which the fabric to be dyed is impregnated with an aqueous disperisonof the dyestuff which contains advantageously l to 50% of urea and athickener, especially sodium alginate, preferably at a temperature notexceeding 60C, and the fabric is then squeezed in the usual manner, ad-

vantageously so that it retains 50 to 100% of liquid referred to itsinitial weight.

For fixing the dyestuff on the impregnated fabric it is heated,advantageously after first having been dried e.g. in a warm current ofair, to a temperature above 100C, e.g. between 180 and 220C.

The above-mentioned thermofixation method is par ticularly suitable fordyeing mixed weaves of polyester fibres and cellulose fibres, especiallycotton. In this case the padding liquor contains in addition to thedyestuff of this invention also dyestuffs suitable for dyeing cotton,for example substantive dyestuffs or vat dyes, or more especially theso-called reactive dyestuffs, that is to say dyestuffs capable offixation by forming a chemical bond with cellulose, for instancedyestuffs containig a chlorotriazine or chlorodiazine ring. In thelatter case it is advantageous to add to the padding li- "quor and acidacceptor, for example, a carbonate,

phosphate, borate or perborate of a alkali metal or a mixture thereof.When dyeing with vat dyes, it is necessary to treat the padded fabric,after it has been heated, with an aqueous alkaline solution of one ofthe reducing agents generally used in vat dyeing.

The dyeings produced by the present processes on polyester fibres areadvantageously subjected to an aftertreatment e.g. by heating in anaqueous solution of a non-ionic detergent.

The dyestuffs of this invention are also suitable for dyeing mixedweaves of polyester fibres and wool; the

wool portion remains reserved and can subsequently be' dyed with a wooldyestuff.

The present dyestuffs are suitable not only for application byimpregnation but also for printing, using e.g. a printing paste thatcontains the finely disperse dyestuff and the usual printing assitants,for example wetting and thickening agents, if required in admixture withone of the cotton dyestuffs mentioned above and if desired in thepresence of urea and/or of an acid acceptor.

The present processes produces stong dyeings and prints having excellentfastness properties, especially good fastness to light, sublimation,decatizing, washing and chlorinated water. They have the furtheradvantages that the dyestuffs to be used according to this inventionreserve well on wool and cotton.

Unless otherwise indicated, parts and percentages in the followingexamples are by weight.

EXAMBLE 1 13.8 Parts of 4-nitroaniline are diazotized in the usualmanner and the resulting diazo solution added to'a mixture of 250 partsof an aqueous solution containing 39.5 parts ofN,N-dimethyl-N-methoxy-N,2-(N- phenyl-N-ethyl)-aminoethyl ammoniumtoluenesulphonate and 500 parts of ice. The coupling mixture is renderedneutral to Congo red with sodium acetate and stirred for 2 hours at 0 5Cto complete the dyestuff formation. After heating to room temperature,the resulting dyestuff of the formula is precipitated with sodiumbromide, suctionedliltercd and dried. lt dyes polyacrylonitrile fibresfast scarlet shades.

When instead of 4-nitroaniline one ofthe diazo components shown inColumn 11 of the following Table is used, the shades listed in Column111 are obtained:

11 Ill EXAMPLE 2 A homogeneous mixture is prepared from 17.2 parts of2-chloro-4-nitroaniline, 15 parts of concentrated hydrochloric acid andparts of ice; 15 parts of concentrated hydrochloric acid and 100 partsof ice are then added followed by 25 parts of a 4N aqueous solution ofsodium nitrite. The whole is stirred for 2 hours, the diazo solution isclarified by filtration and poured into a mixture of 21 parts ofN-methylN,2-(N'-phenyl- 19 N'-ethyl)-aminoethyl-methoxyamine, 50 partsof glacial acetic acid and 300 parts of ice. The coupling mixture isrendered neutral to Congo red by dropping in within one hour aconcentrated aqueous solution of sodium acetate, and the dyestuff issuctioned-filtered, washed with water and dried.

The resulting dyestuff of the formula dyes polyethylene terephthalateand cellulose acetate fibres fast red shades.

The N-methyl-N,2-(N-phenyl-N-ethyl)-aminoethylmethoxyamine used ascoupling component may be prepared in the following manner: A mixture of159 parts of N-ethyl-N,2-hydroxyethylaniline toluenesulphonic acid esterand 270 parts of an alcoholic solution containing 61 parts ofN-methyl-N-methoxyamine is stirred for 1% hours at 70 80C, 50 parts ofsodium bicarbonate are added, the excess N-methyl-N- methoxyaminetogether with 100 parts of alcohol is distilled off, the residuefiltered, the alcoholic filtrate diluted with water and extracted withether. The whole is then evaporated and the residue distilled at 72Cunder a vacuum of 0.03 mm Hg.

EXAMPLE 3 The procedure was the same as in Example 2, except' that thediazo component was 13.8 parts of 4- nitroaniline instead of2-chloro-4-nitraniline. After coupling the dyestuff of the formula OCHis obtained which dyes polyester and cellulose acetate fibres brilliantscarlet shades.

EXAMPLE 4 A solution of 8 parts of the dyestuff described in Example 2in 100 parts of chlorobenzene is mixed with 5 parts of dimethyl sulphateand stirred for 3 hours at 120C, allowed to cool, filtered and thequaternated dyestuff is washed with benzene and petroleum ether. Inwater it gives a clear red solution; it dyes polyacrylonitrile fibresred tints of very good fastness to light.

EXAMPLE 5 A mixture of 7.1 parts of the dyestuff obtained as describedin Example 3, 4 parts of para-toluenesulphonic acid methyl ester and 100parts of anhydrous chlorobenzene is stirred for 6 hours at 120C. Afterworking up as described in Example 4 a dyestuff in which the cation isidentical with that of Example 1 is obtained.

EXAMPLE 6 A mixture of 34.4 parts of the resulting N-cyanoethyl-N-para-toluenesulphonyloxy-ethylaniline and 15.1 parts ofN,N-dimethyl-N-benzyloxyamine is stirred for 7 hours at about C. Thereaction product obtained in this manner is used as it is for thefurther reaction.

39 Parts by volume of concentrated hydrochloric acid and 17.25 parts of2-c hloro-4-nitroaniline are intimately mixed in a mortar dish and thenstirred into 400 parts of ice and water. 25 Parts by volume of 4N sodiumnitrite solution are dropped in at 0 to 5C and the whole stirred until aclear diazo solution forms which is then added to a solution containingthe coupling component obtained as described above (49.5 parts) in 70parts of alcohol. The coupling mixture is rendered neutral to Congo redwith sodium acetate solution. On completion of the coupling reaction thedyestuff is precipitated with sodium chloride, suctioned-filtered,dissolved in hot water and the solution filtered clear. The dyestuff ofthe formula is salted out, filtered and dried. lt dyes polyacrylonitrilefibres stong scarlet shades having very good fastness properties.

EXAMPLE 7 A mixture of 13.8 parts of 4-nitroaniline, 30 parts by volumeof water and 30 parts by volume of concentrated hydrochloric acid isheated at 60 70C until a clear solution is formed. The parts of ice areadded and at 0C 7 parts of sodium nitrite are aded all at once. Afterstirring for 10 minutes the diazotization is complete. The diazosolution is poured into a solution of 29 parts of the methanesulphonicacid ester of 3-(N- methyl-N,2'-hydroxyethyl)-aminoacetanilide in 300parts of glacial acetic acid. At 0 5C within 30 minutes the whole isrendered neutral to Congo red with 70 parts of a 4N sodium acetatesolution and the coupling mixture diluted with 600 parts of ice water.The dyestuff thus formed is suctioned-filtered, washed free from aceticacid with water and dried at a low temperature under vacuum. A mixtureof 22 parts of this dyestuff, 200 parts of ethanol and 7.5 parts ofisoxalidine is refluxed for 7 hours, the reaction mixture then pouredinto 1,000 parts of water and 5 parts of 30% aqueous sodium hydroxidesolution are added. The completely precipitated dyestuff of the formulais suctioned-filtered and dried. it dyes cellulose acetate fibres clearred tints.

EXAMPLE 8 of 25 parts of 36% hydrochloric acid and 250 parts of icewater is rapidly mixed at 0 5C with a solution of 7 parts of sodiumnitrite in 20 parts of water. On completion of the diazotization a smallexcess of nitrous acid is decomposed by adding 0.2 part of sulphamicacid, and the mixture is then run into a mixture of 13 parts ofZ-methylindole, 150 parts ofglacial acetic acid, 50 parts of ice and 15parts of crystalline sodium ace tate. After stirring for 2 hours thebatch is diluted with 600 parts of water and the dyestuff salted outwith 30 parts of sodium chloride, filtered and dried. An orange dyestuffpowder is obtained which dyes polyacryloni trile fibres from an aqueousbath fast yellow tints.

The diazo component is manufactured by condensing4-acetylamino-a-chloroacetophenone with N,N- dibutoxyamine, followed byhydrolysis of the acetyl group by boiling for 2 hours in 2N hydrochloricacid.

When 2-methylindole is replaced by the coupling components listed inColumn 11 of the following Table, further dyestuffs are obtained whichdye polyacrylonitrile fibres the shades shown in Column III.

HIGH. 1

O Nil-Q025 H OC H dyes polyester fibres brilliant blue shades.

EXAMPLE 11 A mixture of 4.5 parts of the dyestuff of Example 10, 100parts of chlorobenzene and 2 parts of dimethyl sul- 0 phate is stirredand heated for 8 hours at 90 100C.

No. Coupling Component (11) Shade on polyacrylonitrile l3-methylpyrazolone-(5) yellow 2 1-phenyl-3-methylpyrazolone-(5) do.

3 lndan-l,3-dione do.

4 N-methyl-N,Z-cyanoethylaniline orange 5 diphenylamine do.

6 Z-naphthylamine scarlet 7 N-ethyl-Z-naphthylamine red 8 Z-naphtholscarlet 9 2-(N,N-bis-cyanoethoxy-ethylamino)- ruby 4-propionylaminoanisole EXAMPLE 9 v A mixture of 105 parts of N-methyl-N,2-

hydroxyethylmethoxyamine (obtained according to Jones and Major, 1. Am.Chem. Soc. 52, 1085 [1930]) in 1,000 parts of anhydrous pyridine ismixed with 190 parts of 4-nitrobenzoylchloride while cooling and thewhole is stirred for 5 hours at 5 10C. the reaction mixture is dilutedwith 5,000 parts of ice water and the precipitated estersuctioned-filtered, dissolved in 3,000 parts of ethanol and hydrogenatedin the presence of a catalytic amount of Raney nickel under atmosphericpressure at room temperature until no more hydrogen is consumed.Evaporation of the alcoholic solution furnishes 4-aminobenz0icacid-2-(Nmethyl-N- methoxyamino)-ethyl ester. 2.24 Parts of this esterare dissolved at 0C in 25 parts by volume of N hydrochloric acid and asolution of 0.7 part of sodium nitrite in 3 parts by volume of water isadded. The resulting diazo solution is added to a solution of 1.3 partsof 3-amino- 4-methoxy-toluene in 15 parts by volume of N hydrochloricacid and 20 parts by volume of 4N sodium acetate solution are dropped inat 0 -5C. The whole is stirred for 3 hours and the precipitated dyestuffsuctioned-filtered, washed with water and again dissolved in 50 parts ofN hydrochloric acid, diazotized at 10C with 10 parts by volume of Nsodium nitrite solution and after 2 hours the diazo solution is pouredinto a solution of 1 part of para cresol in 100 parts of water, 2 partsby volume of concentrated sodium hydroxide solution and 10 parts ofsodium carbonate. On completion of the coupling reaction the dyestuff issuctionedfiltered, washed with water and dried. It dyes polyethyleneterephthalate fibres fast orange tints.

EXAMPLE 10 A mixture of 7.8 parts of l-methylamino-4-(4'-methyl3'-chloromethyl)-phenylaminoanthraquinone The quaternated dyestuffsalt which crystallizes out on cooling dyes polyacrylonitrile fast bluetints. Similar blue dyestuffs are obtained when dimethyl sulphate isreplaced by diethyl sulphate or para-toluenesulphonic acid butyl ester.

EXAMPLE 12 4 Parts of the dyestuff of the formula 0 OH i 0 NHZQaucoczgcn.

are dissolved in 50 parts of dimethylformamide and 2 parts ofN,N-dimethylbutoxyamine are added. The mixture is stirred at C until aspecimen has become completely water-soluble. The batch is then dilutedwith 400 parts of water and from the aqueous solution the dyestuff isprecipitated with 40 parts of sodium chloride. On polyacrylonitrile itproduces fast violet dyeings.

EXAMPLE 13 A mixture of 25 parts of 5-amino-l ,9isothiazole anthrone, 16parts of 3N-methyl-N-methoxyaminopropionylchloride and 500 parts ofchlorobenzene is stirred for 2 hours at C and the chlorobenzene isdistilled off with steam, to yield the dyestuff of the formula whichdyes polyester fibres fast yellow shades.

EXAMPLE 14 17 Parts of l-hydroxy-4-p-toluidinoanthraquinone are added at10 15C to 50 parts of chlorosulphonic acid and the whole is stirred atthis temperature for 4 hours. The blue solution is poured over ice andthe blue or: O-CH 1 so 0o r; 1? ca 2 24 2 l OH2-CH2/ issuctioned-filtered, washed free from pyridine with water and dried. Itdyes polyester fibres from an aqueous dispersion fast violet shades.

EXAMPLE 15 A mixture of 25.5 parts of N,N-dimethyl-N,2-(N-ethyl-N,p-aminophenyl)-aminoethyl benzoyloxy ammonium toluenesulphonate[obtainable by nitrosation of the coupling component described inExample 6 and reduction with zinc dust], 10 parts of2,4-dinitrochlorobenzene and 200 parts of ethanol is refluxed for 5hours. On cooling, the dyestuff crystallizes out and issuctioned-filtered and dried. lt dyes polyacrylonitrile fibres fastyellowish brown shades.

A dyestuff having similar properties is obtained when parts of4-chloro-3-nitrobenzenesulphonylanilide are used instead of2,4-dinitrochlorobenzene.

EXAMPLE 16 Parts of phosphorus oxychloride are dropped into 17.5 partsof dimethylformamide while cooling. The 22.2 parts ofN-methy-N,2-(N'-ethyl-N,3'-toluyl)- aminoethylmethoxyamine are slowlyadded to the resulting mixture at a rate such that the temperature doesnot exceed 60C and the whole is then further stirred for 6 hours at 60C,poured into 500 parts of ice water and adjusted to a pH value of 9 withconcentrated sodium hydroxide solution. The emulsion is extracted withchloroform and the aldehyde is isolated by evaporating the chloroformsolution.

A mixture of 25 parts of the aldehyde, 7.3 parts of malodinitrile, 100parts of methanol and 1 part of piperidine is refluxed for 4 hours, andthen 60 parts of methanol are distilled off. On cooling, the dyestuff ofthe formula crystallizes out. It dyes polyester and cellulose acctatefibres fast, greenish yellow shades.

EXAMPLE l7 17 Parts of the dyestuff described in Example l6 aredissolved at C in 50 parts by volume of dimethylformamide and 13 partsof dimethyl sulphate are slowly added at this temperature. Afterstirring for 2 hours at 80C a specimen forms a clear aqueous solution.On addition of parts of ethyl acetate the dyestuff salt is obtained incyrstalline form. On polyacrylonitrile fibres it produces greenishyellow dyeings having excellent fastness to light.

We claim: 1. A dyestuff of the formula 3x h) f 7 L. l l I l X 0 N-R --NR a l R; x

in which n is l or 2,

X is NH or OH,

X and X each independently is hydrogen, NH- OH or N0 R is methylene,ethylene, phenylene, toluylcne Y is alkylene of at most 4 carbon atoms,

R is hydrogen or alkyl of at most 3 carbon atoms,

R is hydrogen, alkyl of at most 3 carbon atoms or benzyl,

R is alkyl of at most 3 carbon atoms, benzyl or cyclohexyl, and

X is an anion.

2. A dyestuff according to'claim l in which X' is a halide.

3. A dyestuff according to claim 1 in which X is chlorine, bromine,iodine, =SO,, S();,alkyl, SO aryl or SO Oalkyl.

4. A dyestuff according to claim 1 of formula HNCH cH N- 00 1i.

2. A dyestuff according to claim 1 in which X is a halide.
 3. A dyestuffaccording to claim 1 in which X is chlorine, bromine, iodine, SO4,-SO3-alkyl, -SO3aryl or -SO3-O-alkyl.
 4. A dyestuff according to claim 1of formula